EP0618238B1 - Wässrige Vernetzungsharzzusammensetzung - Google Patents

Wässrige Vernetzungsharzzusammensetzung Download PDF

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EP0618238B1
EP0618238B1 EP93105241A EP93105241A EP0618238B1 EP 0618238 B1 EP0618238 B1 EP 0618238B1 EP 93105241 A EP93105241 A EP 93105241A EP 93105241 A EP93105241 A EP 93105241A EP 0618238 B1 EP0618238 B1 EP 0618238B1
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aqueous
weight
monomer
unit
resin
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French (fr)
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EP0618238A1 (de
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Masahiro C/O Mitsubishi Yuka Aoki
Takeo C/O Mitsubishi Yuka Tsukamoto
Ryutaro C/O Mitsubishi Yuka Hayashi
Yoshinori C/O Mitsubishi Yuka Kato
Takeshi C/O Mitsubishi Yuka Awata
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Mitsubishi Chemical BASF Co Ltd
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Mitsubishi Chemical BASF Co Ltd
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Priority claimed from JP28935691A external-priority patent/JP2920577B2/ja
Application filed by Mitsubishi Chemical BASF Co Ltd filed Critical Mitsubishi Chemical BASF Co Ltd
Priority to DE69306750T priority Critical patent/DE69306750T2/de
Priority to EP93105241A priority patent/EP0618238B1/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups

Definitions

  • This invention relates to an aqueous crosslinking resin composition which readily undergoes a crosslinking reaction at room temperature to provide a crosslinked film excellent in water resistance, solvent resistance, adhesion to a substrate, such as a metal, an inorganic material, a plastic article, a coated article, etc., and hardness.
  • An aqueous crosslinking resin composition comprising a carbonyl-containing resin aqueous emulsion obtained by emulsion copolymerization of a monomer containing a carbonyl group based on an aldo group or a keto group and a hydrazine derivative having at least two hydrazino groups (-NHNH 2 ) per molecule is known as disclosed, e.g., in JP-A-54-144432 (corresponding to U.S. Patent 4,267,091) (the term "JP-A" as used herein means an "unexamined published Japanese patent application”).
  • the resin composition of this type is advantageous in that it has room temperature crosslinkability and is of one-pack type easy to use, but still needs further improvement in terms of film properties, such as adhesion to a substrate, and water resistance,
  • EP-A 0 219 046 discloses storage stable crosslinkable resin compositions obtained by reaction of (A) polymeric organic compounds having carbonyl groups in the presence of (B) monoketones and/or monoaldehydes with (C) polyhydrazides.
  • EP-A 0 005 167 discloses binder for paints comprising (A) an emulsion of a copolymer, (B) an aliphatic dihydrazine compound and (C) a water-soluble salt of zinc, manganese, cobalt and/or lead.
  • CHEMICAL ABSTRACTS volume 96 (1982) No. 24 201 337w discloses aqueous dispersions of carbonyl group containing copolymer granules containing hydrazine derivatives for coatings having good strength.
  • An object of the present invention is to provide an aqueous crosslinking resin composition which provides a crosslinked film having markedly improved adhesion to a substrate, well-balanced resistance to water and solvents, and hardness.
  • the present invention relates to an aqueous crosslinking resin composition
  • an aqueous crosslinking resin composition comprising (I) an aqueous resin dispersion obtained by emulsion polymerization of a monomer mixture consisting of (a) 0.5% to 50% by weight of an unsaturated carboxylic acid monomer, (b) 0.5% to 60% by weight of a carbonyl-containing unsaturated monomer containing at least one carbonyl group based on an aldo group or a keto group, and (c) 30% to 99% by weight of other unsaturated monomer(s) copolymerizable with monomers (a) and (b), and (II) a hydrazine derivative having at least two hydrazino groups (-NHNH 2 ) per molecule, wherein the resin content in the aqueous resin dispersion (I) has been solubilized to a degree of at least 5% by weight by addition of an alkali and/or an organic solvent.
  • Aqueous resin dispersion (I) which can be used in the present invention is an aqueous dispersion of a copolymer resin obtained by emulsion polymerization of a specific monomer mixture comprising monomers (a) to (c).
  • Unsaturated carboxylic acid monomer (a) includes unsaturated mono- and polycarboxylic acids having from 3 to 5 carbon atoms, such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid. These unsaturated carboxylic acid monomers may be used either individually or in combination of two or more thereof.
  • Monomer (a) is used in an amount of not less than 0.5% by weight, not more than 50% by weight, and preferably from 2 to 30% by weight, based on the monomer mixture. If the proportion of monomer (a) is less than 0.5% by weight, sufficient solubilization of the dispersed resin by addition of an alkali and/or an organic solvent cannot be achieved. If it is more than 50% by weight, the crosslinked film exhibits improved solvent resistance but tends to have reduced water resistance.
  • Carbonyl-containing unsaturated monomer (b) is a polymerizable unsaturated compound containing at least one carbonyl group based on an aldo group or a keto group (hereinafter simply referred to as a carbonyl-containing unsaturated monomer). Therefore, polymerizable unsaturated monomers which contain a carbonyl group based on a carboxyl group, a carboxylic acid ester group, a carboxylic acid amido group, etc. are not included under carbonyl-containing unsaturated monomer (b).
  • carbonyl-containing unsaturated monomer (b) examples include acrolein, diacetone acrylamide, formylstyrol, a vinyl alkyl ketone having from 4 to 7 carbon atoms (e.g., vinyl methyl ketone, vinyl ethyl ketone or vinyl butyl ketone), diacetone acrylate, acetonitrile acrylate, diacetone methacrylate, 2-hydroxypropyl acrylate acetylacetate, and butanediol-1,4-acrylate acetylacetate, and a (meth)acryloxyalkylpropenal represented by formula: wherein R 1 represents a hydrogen atom or a methyl group; R 2 represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms; R 3 represents an alkyl group having from 1 to 3 carbon atoms; and R 4 represents an alkyl group having from 1 to 4 carbon atoms. Preferred of them are diacetone acrylamide
  • Carbonyl-containing unsaturated monomer (b) is used in an amount of not less than 0.5% by weight, not more than 60% by weight, and preferably from 5 to 50% by weight, based on the monomer mixture. If the proportion of monomer (b) is less than 0.5% by weight, the crosslink density achieved by the reaction with hydrazine derivative (II) is reduced, and the physical properties of the crosslinked film, such as water resistance and solvent resistance, are insufficient as a result. If the proportion of monomer (b) is more than 60% by weight, no further improvements can be obtained.
  • copolymerizable unsaturated monomer (c), selected from those exclusive of monomers (a) and (b), includes alkyl acrylates or methacrylates having from 1 to 8 carbon atoms in the alkyl moiety thereof (e.g., methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, or t-butyl ester of acrylic acid or methacrylic acid), glycidyl methacrylate, glycol mono- or diacrylates, glycol mono- or dimethacrylates, aromatic vinyl compounds (e.g., styrene), vinyl halides (e.g., vinyl chloride and vinyl bromide), vinylidene chloride, acrylonitrile, methacrylonitrile, and saturated carboxylic acid vinyl esters (e.g., vinyl acetate and vinyl propionate).
  • unsaturated carboxylic acid amides e.g., acrylamide, methacrylamide, and itaconic acid amide
  • N-alkyl and/or N-alkylol derivatives of unsaturated carboxylic acid amides e.g., N-methylacrylamide, N-isobutylacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, and N-ethoxymethylacrylamide
  • unsaturated sulfonic acids e.g., vinylsulfonic acid and methylacrylamidepropanesulfonic acid
  • hydroxyl-containing unsaturated monomers e.g., hydroxyethyl methacrylate and hydroxypropyl acrylate
  • unsaturated monomers e.g., hydroxyethyl methacrylate and hydroxypropyl acrylate
  • These monomers are effective to ensure solubilization of the resulting dispersed resin by addition of an alkali and/or an organic solvent.
  • unsaturated monomers (c) may be used either individually or in combination of two or more thereof and are selected appropriately according to a degree of solubilization as desired and the end use of the resulting aqueous crosslinking resin composition.
  • Unsaturated monomers (c) are used in a total proportion of not more than 99% by weight, not less than 30% by weight, based on the monomer mixture.
  • Emulsion polymerization for preparing aqueous resin dispersion (I) can be carried out by (A) a method of using an ordinary emulsifying agent or (B) a method of using a copolymer dispersant, and particularly a water-soluble or alkali-soluble carbonyl-containing copolymer dispersant.
  • Emulsifying agents which can be used in method (A) include anionic surface active agents, such as higher alcohol sulfates, alkylbenzenesulfonates, polyoxyethylene alkylsulfates, polyoxyethylene alkylphenol ether sulfates, vinylsulfonates, and vinylsulfosuccinates; and nonionic surface active agents, such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, ethylene oxide-propylene oxide block copolymers, and sorbitan derivatives.
  • anionic surface active agents such as higher alcohol sulfates, alkylbenzenesulfonates, polyoxyethylene alkylsulfates, polyoxyethylene alkylphenol ether sulfates, vinylsulfonates, and vinylsulfosuccinates
  • nonionic surface active agents such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, ethylene oxide-propylene oxide block copo
  • the copolymer dispersant which can be used in method (B) preferably includes copolymers comprising (i) from 0.5 to 99.5% by weight of a carbonyl-containing monomer unit having at least one carbonyl group based on aldo or keto group and one polymerizable double bond per molecule, (ii) from 0.5 to 99.5% by weight of a monomer unit selected from the group consisting of a unit derived from a mono-olefinic unsaturated carboxylic acid having from 3 to 5 carbon atoms, a unit derived from a mono-olefinic unsaturated carboxylic acid amide having from 3 to 5 carbon atoms, a unit derived from an N-alkyl and/or N-alkylol derivative of a mono-olefinic unsaturated carboxylic acid amide having from 3 to 5 carbon atoms, and an amino-containing monomer unit (e.g., N,N-dimethylaminoethyl methacrylate and N,
  • the copolymer dispersant can easily be prepared by emulsion polymerization of a monomer mixture comprising monomers (i) to (iii) in substantially the same proportion as mentioned above in water or an organic solvent, if desired, in the presence of an alkali, e.g., NaOH or aqueous ammonia.
  • an alkali e.g., NaOH or aqueous ammonia.
  • Emulsion polymerization in accordance with either method (A) or (B) is conducted in an aqueous medium in the presence of a polymerization initiator.
  • Polymerization initiators which can be used preferably include persulfates, such as potassium persulfate and ammonium persulfate; peroxides, such as hydrogen peroxide, benzoyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide; and azobisisobutyronitrile.
  • persulfates such as potassium persulfate and ammonium persulfate
  • peroxides such as hydrogen peroxide, benzoyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide
  • azobisisobutyronitrile azobisisobutyronitrile.
  • water-soluble initiators and redox initiators are preferred.
  • the aqueous crosslinking resin composition containing aqueous resin dispersion (I) prepared by method (B) is superior to that containing aqueous resin dispersion (I) prepared by method (A) in terms of physical properties of the crosslinked film.
  • a chain transfer agent is preferably used in emulsion polymerization, either by method (A) or by method (B).
  • aqueous resin dispersion (I) is prepared in the presence of a chain transfer agent
  • the resulting aqueous crosslinking resin composition exhibits markedly improved film properties, especially adhesion to a substrate, probably because presence of a chain transfer agent reduces the molecular weight of the copolymer resin produced, which seems to facilitate the solubilization with an alkali and/or an organic solvent.
  • chain transfer agents commonly employed for homo- or copolymerization of vinyl monomers can be employed.
  • suitable chain transfer agents include mercaptan compounds, e.g., methyl mercaptan, t-butyl mercaptan, decyl mercaptan, benzyl mercaptan, lauryl mercaptan, stearyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptoacetic acid, and mercaptopropionic acid; alcohols, e.g., methyl alcohol, n-propyl alcohol, isopropyl alcohol, t-butyl alcohol, benzyl alcohol, and allyl alcohol; hydrocarbons, e.g., ethylbenzene and cumene; and halogenated hydrocarbons, e.g., chloroethane, chloroform, carbon tetrachloride
  • the amount of the chain transfer agent used greatly influences solubilization of the dispersed resin. With the composition of the resin being equal, the larger the amount of the chain transfer agent, the more readily is the dispersed resin solubilized, leading to an increase in adhesion of the crosslinked film to a substrate. However, too high a level of addition results in reduction in water resistance and solvent resistance.
  • a suitable amount of the chain transfer agent is usually from 0.01 to 3 parts by weight per 100 parts by weight of the solid resin content.
  • the aqueous crosslinking resin composition of the present invention can be prepared by mixing the thus prepared aqueous resin dispersion (I) with hydrazine derivative (II) having at least two hydrazino groups per molecule and by adding an alkali and/or an organic solvent to solubilize the resin content of aqueous resin dispersion (I) to a degree of at least 5% by weight.
  • Solubilization i.e., addition of an alkali and/or an organic solvent, may be conducted before the commencement of emulsion polymerization for the preparation of aqueous resin dispersion (I), or before, simultaneously with, or after mixing of aqueous resin dispersion (I) and hydrazine derivative (II).
  • degree of solubilization means a value determined as follows.
  • aqueous resin dispersion is prepared under quite the same conditions as actually used for preparing an aqueous crosslinking resin composition of the present invention, except for using no hydrazine derivative (II).
  • the resulting resin dispersion is diluted with water so as to have a nonvolatile content of 15% by weight.
  • the nonvolatile content (W) of the resulting diluted resin dispersion is measured.
  • the diluted resin dispersion is centrifuged at 1.8 x 10 5 g (acceleration of gravity) for 60 minutes, and the nonvolatile content (w) in the supernatant liquid is measured.
  • Alkalis which can be used for solubilization include inorganic water-soluble alkalis, e.g., sodium hydroxide and potassium hydroxide; inorganic salts capable of providing an alkaline aqueous solution, e.g., sodium hydrogencarbonate and sodium pyrophosphate; aqueous ammonia; and organic amines.
  • inorganic water-soluble alkalis e.g., sodium hydroxide and potassium hydroxide
  • inorganic salts capable of providing an alkaline aqueous solution e.g., sodium hydrogencarbonate and sodium pyrophosphate
  • aqueous ammonia aqueous ammonia
  • organic amines organic amines.
  • Organic solvents which can be used for solubilization include those compatible with water and those incompatible with water but considerably soluble in water, such as alcohols, e.g., methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and ethylene glycol; cellosolves, e.g., methyl cellosolve, ethyl cellosolve, and butyl cellosolve, and esters thereof; carbitols, e.g., methylcarbitol, ethylcarbitol, and butylcarbitol, and esters thereof; tetrahydrofuran, dioxane, dimethylformamide, and ethyl acetate.
  • alcohols e.g., methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol
  • Solubilization may be effected by addition of the above-mentioned alkali alone, the above-mentioned organic solvent alone, or both of them.
  • a preferred degree of solubilization is 10% by weight or more.
  • Hydrazine derivative (II) containing at least two hydrazino groups (hydrazine residual groups) per molecule includes dicarboxylic acid dihydrazides having from 2 to 10, and preferably from 4 to 6, carbon atoms, which are dehydrating condensation products between a dicarboxylic acid and hydrazine (e.g., oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, and itaconic acid dihydrazide); and water-soluble aliphatic dihydrazines having from 2 to 4 carbon atoms (e.g., ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, and butylene-1,4-dihydrazine).
  • JP-A-55-6535 corresponding to U.S. Patent 4,230,525).
  • the aqueous crosslinking resin composition according to the present invention may further contain other aqueous resin dispersions, such as an aqueous resin dispersion obtained by general emulsion polymerization or a urethane resin emulsion, as long as the film properties of the composition are not impaired.
  • aqueous resin dispersions such as an aqueous resin dispersion obtained by general emulsion polymerization or a urethane resin emulsion, as long as the film properties of the composition are not impaired.
  • the aqueous crosslinking resin composition of the present invention may furthermore contain various additives, such as dispersants, lubricants, anti-foaming agents, solvents, film formation aids, plasticizers, anti-freezing agents, thickeners, air entrainers, water reducing agents, quick-setting agents, crosslinking accelerators, retarders, and tackifiers.
  • additives such as dispersants, lubricants, anti-foaming agents, solvents, film formation aids, plasticizers, anti-freezing agents, thickeners, air entrainers, water reducing agents, quick-setting agents, crosslinking accelerators, retarders, and tackifiers.
  • the aqueous crosslinking resin composition of the present invention finds various uses, with its crosslinkability being taken advantage of, as not only coating compounds but adhesives for plywood, woodworking adhesives, pressure-sensitive adhesives for paper or tapes, and fiber coating compounds.
  • resin dispersion A In a reactor equipped with a temperature controller, an anchor stirrer, a reflux condenser, a feeder, a thermometer, and an inlet for nitrogen was charged 200 parts of water, and the reactor was then purged with nitrogen. The inner temperature was raised to 90°C, and mixture I having the following composition and an initiator solution comprising 2.5 parts of potassium persulfate and 85 parts of water were continuously fed to the reactor in small portions over a period of 3.5 hours to conduct a polymerization reaction. After completion of the addition, the mixture was kept at 90°C for an additional period of 2 hours to complete the reaction to obtain an aqueous resin dispersion having a solids content of 50% (hereinafter designated resin dispersion A).
  • Composition of Mixture I Water 200 parts Sodium salt of a sulfuric acid half-ester of an ethylene oxide (20 mol) adduct of p-nonyl phenol (hereinafter referred to as anionic emulsifying agent A) (35% aqueous solution) 30 parts Ethylene oxide (25 mol) adduct of p-nonyl phenol (hereinafter referred to as nonionic emulsifying agent B) (20% aqueous solution) 20 parts Methyl methacrylate 200 parts Butyl acrylate 140 parts Diacetone acrylamide 40 parts Acrylic acid 20 parts
  • Aqueous resin dispersions (designated resin dispersion B to G) were prepared in the same manner as for resin dispersion A of Preparation Example 1, except for changing the kinds and amounts of the unsaturated monomers and the dispersant as shown in Table 1 below.
  • Aqueous resin dispersions (designated resin dispersion H to J) were prepared in the same manner as for resin dispersion A of Preparation Example 1, except for changing the kinds and amounts of the unsaturated monomers and the dispersant as shown in Table 2 below and a chain transfer agent as shown in the Table being added to composition of mixture.
  • Composition of Mixture II Methyl methacrylate 180 parts Butyl acrylate 150 parts Diacetone acrylamide 60 parts Methacrylic acid 10 parts t-Dodecylmercaptan (chain transfer agent) 0.1 part Composition of Mixture III: Water 120 parts Sodium persulfate 2.5 parts Sodium hydroxide 4 parts
  • Aqueous resin dispersions (designated resin dispersions L and M) were prepared in the same manner as in Preparation Example 11, except for replacing the copolymer dispersant CD-1 with a 25% alkaline aqueous solution of a methyl acrylate/diacetone acrylamide/acrylic acid copolymer (20/20/60; molecular weight: ca. 6,000) (hereinafter referred to as CD-2) and also changing the kinds and amounts of the unsaturated monomers and chain transfer agent as shown in Table 2.
  • CD-1 a 25% alkaline aqueous solution of a methyl acrylate/diacetone acrylamide/acrylic acid copolymer (20/20/60; molecular weight: ca. 6,000)
  • composition of the polymerization system used for the preparation of resin dispersions A to M and resin solution N and the solids content of these resin dispersions or solution are shown in Tables 1 and 2 below.
  • Nonvolatile content means a weight percentage of a residue when a resin composition is dried at 120°C for 30 minutes.
  • Crosslinking resin compositions were prepared in the same manner as in Example 1, except for making the alterations shown in Tables 3 to 5 below (the resin composition of Comparative Example 2 was non-crosslinking composition).
  • the resin composition was coated on a glass plate to a dry thickness of 500 ⁇ m and dried at 20°C for 1 week.
  • the dry film was punched to prepared a 5-by-5 cm square specimen.
  • the specimen was immersed in water at 20°C for 1 day, and the water absorption (wt%) was measured.
  • the resin composition was coated on a polypropylene plate (hereinafter abbreviated as PP plate) or a polyester plate (hereinafter abbreviated as PET plate) to a dry thickness of 20 ⁇ m and dried at 20°C for 1 week.
  • PP plate polypropylene plate
  • PET plate polyester plate
  • a peel test of the dry film on the substrate was conducted using an adhesive tape "Cello-Tape" (produced by Nichiban Co., Ltd.), and the results were rated as follows.
  • the resin composition was coated on a steel plate to a dry thickness of 20 ⁇ m and dried at 20°C for 1 week.
  • the film on the substrate was scratched with a pencil to evaluate hardness according to JIS K-5400.
  • the aqueous crosslinking resin composition according to the present invention easily undergoes crosslinking between a carbonyl group and a hydrazino group at room temperature to form a crosslinked film.
  • the crosslinked film exhibits excellent adhesion to a substrate, well-balanced resistance to water and solvents, and satisfactory hardness. Therefore, the aqueous crosslinking resin composition of the invention is highly useful as primers for plastics and metals, coating compounds for repairs of coatings.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
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Claims (8)

  1. Wäßrige vernetzende Harzzusammensetzung, umfassend (I) eine wäßrige Harzdispersion, erhalten durch Emulsionspolymerisation einer Monomerenmischung, bestehend aus (a) 0,5 bis 50 Gew.-% eines ungesättigten Carbonsäuremonomers, (b) 0,5 bis 60 Gew.-% eines Carbonyl-enthaltenden ungesättigten Monomers, das mindestens eine Carbonylgruppe auf der Basis einer Aldogruppe oder einer Ketogruppe enthält, und (c) 30 bis 99 Gew.-% eines anderen ungesättigten Monomers (anderer ungesättigter Monomerer), das (die) mit den Monomeren (a) und (b) copolymerisierbar ist, und (II) ein Hydrazinderivat, das mindestens zwei Hydrazinogruppen (-NHNH2) pro Molekül aufweist, und worin der Harzgehalt in der wäßrigen Harzdispersion (I) bis zu einem Grad von mindestens 5 Gew.-% durch Zugabe von Alkali- und/oder einem organischen Lösungsmittel solubilisiert ist.
  2. Wäßrige vernetzende Harzzusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die wäßrige Harzdispersion (I) eine Harzdispersion ist, die erhalten wurde durch Emulsionspolymerisation einer Monomerenmischung bestehend aus 2 bis 30 Gew.-% des Monomers (a), 5 bis 50 Gew.-% des Monomers (b) und des Monomers (c).
  3. Wäßrige vernetzende Harzzusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die wäßrige Harzdispersion (I) eine Harzdispersion ist, die durch Emulsionspolymerisation in Gegenwart eines Kettenübertragungsreagens erhalten wurde.
  4. Wäßrige vernetzende Harzzusammensetzung nach Anspruch 3, dadurch gekennzeichnet, daß das Kettenübertragungsreagens in einer Menge von 0,01 bis 3 Gew.-Teilen pro 100 Gew.-Teile des festen Harzgehaltes vorhanden ist.
  5. Wäßrige vernetzende Harzzusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß der Harzgehalt in der wäßrigen Harzzusammensetzung (I) bis zu einem Grad von 10 Gew.-% oder mehr solubilisiert ist.
  6. Wäßrige vernetzende Harzzsammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Molverhältnis der Hydrazinogruppe im Hydrazinderivat (II) zur Carbonylgruppe im Harz der wäßrigen Harzdispersion (I) 0,05 bis 5 beträgt.
  7. Wäßrige vernetzende Harzzusammensetzung nach Anspruch 6, dadurch gekennzeichnet, daß das Molverhältnis der Hydrazinogruppe im Hydrazinderivat (II) zur Carbonylgruppe im Harz der wäßrigen Harzdispersion (I) 0,4 bis 1,2 beträgt.
  8. Wäßrige vernetzende Harzzusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die wäßrige Harzdispersion (I) eine Harzdispersion ist, die erhalten wurde durch Emulsionspolymerisation, bei der als Dispergiermittel ein Copolymer verwendet wird, umfassend (i) 0,5 bis 99,5 Gew.-% einer Carbonyl-enthaltenden Monomereinheit mit mindestens einer Carbonylgruppe auf der Basis einer Aldo- oder Ketogruppe und einer polymerisierbaren Doppelbindung pro Molekül, (ii) 0,5 bis 99,5 Gew.-% einer Monomereinheit, ausgewählt aus der Gruppe bestehend aus einer von einer monoolefinisch ungesättigten Carbonsäure mit 3 bis 5 Kohlenstoffatomen abgeleiteten Einheit, einer von einem monoolefinisch ungesättigten Carbonsäureamid mit 3 bis 5 Kohlenstoffatomen abgeleiteten Einheit, einer von einem N-Alkyl und/oder N-Alkylolderivat eines monoolefinisch ungesättigten Carbonsäureamids mit 3 bis 5 Kohlenstoffatomen abgeleiteten Einheit und einer Aminoenthaltenden Monomereinheit, und (iii) nicht mehr als 70 Gew.-% einer Monomereinheit, ausgewählt aus der Gruppe bestehend aus einer Alkylacrylat- oder Alkylmethacrylat-Einheit mit 1 bis 8 Kohlenstoffatomen in ihrem Alkylteil, einer aromatischen Vinylmonomer-Einheit, einer Vinylhalogenid-Einheit, einer Ethylen-Einheit, einer Acrylnitril-Einheit, einer gesättigten Carbonsäurevinylester-Einheit, einer Hydroxylenthaltenden Monomereinheit und einer 1,3-Dien-Einheit.
EP93105241A 1991-10-09 1993-03-30 Wässrige Vernetzungsharzzusammensetzung Expired - Lifetime EP0618238B1 (de)

Priority Applications (2)

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DE69306750T DE69306750T2 (de) 1993-03-30 1993-03-30 Wässrige Vernetzungsharzzusammensetzung
EP93105241A EP0618238B1 (de) 1991-10-09 1993-03-30 Wässrige Vernetzungsharzzusammensetzung

Applications Claiming Priority (2)

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JP28935691A JP2920577B2 (ja) 1991-10-09 1991-10-09 水性架橋性樹脂組成物
EP93105241A EP0618238B1 (de) 1991-10-09 1993-03-30 Wässrige Vernetzungsharzzusammensetzung

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EP0618238A1 EP0618238A1 (de) 1994-10-05
EP0618238B1 true EP0618238B1 (de) 1996-12-18

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US6251973B1 (en) 1998-11-23 2001-06-26 Akzo Nobel N.V. Coatings and coating compositions of a reactive group-containing polymer, a hydrazide and a silane
JP2002356643A (ja) * 2001-05-30 2002-12-13 Kansai Paint Co Ltd 水性塗料用樹脂組成物
JP2003096386A (ja) * 2001-09-26 2003-04-03 Kansai Paint Co Ltd 水性塗料用樹脂組成物
EP1799782B1 (de) * 2004-10-08 2012-12-12 The Sherwin-Williams Company Selbstvernetzende wässrige beschichtungen
CN102101929B (zh) 2009-12-18 2013-10-16 罗门哈斯公司 可固化水性组合物

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GB1421130A (en) * 1972-11-16 1976-01-14 Harlow Chemical Ltd Surface coating compositions
DE2819092A1 (de) * 1978-04-29 1979-11-08 Basf Ag Bindemittel fuer anstrichmittel
DE3536262A1 (de) * 1985-10-11 1987-04-16 Basf Ag Lagerstabile, in organischem loesemittel geloeste oder dispergierte vernetzbare zusammensetzungen, ihre herstellung und verwendung

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